QUESTIONS AND EXERCISES 13

0.8 Calculate the minimum energy that a bird of mass 25 g

must expend in order to reach a height of 50 m.
0.9 The unit 1 electronvolt (1 eV) is defined as the energy
acquired by an electron as it moves through a potential dif-
ference of 1 V. Express 1 eV in (a) joules, (b) kilojoules per mole.
0.10 Calculate the work done by (a) one electron, (b) 1 mol e

as they move between the electrodes of a commercial cell

rated at 1.5 V.
0.11 You need to assess the fuel needed to send the robot
explorer Spirit, which has a mass of 185 kg, to Mars. (a) What
was the energy needed to raise the vehicle itself from the
surface of the Earth to a distant point where the Earths
gravitation field was effectively zero? The mean radius of the
Earth is 6371 km and its average mass density is 5.517 g cm
3
.
Hint : Use the full expression for gravitational potential energy
in Exercise 0.35.
0.12 Express (a) 108 kPa in torr, (b) 0.975 bar in atmo-
spheres, (c) 22.5 kPa in atmospheres, (d) 770 Torr in pascals.
0.13 Calculate the pressure in the Mindaao trench, near the
Philippines, the deepest region of the oceans. Take the depth
there as 11.5 km and for the average mass density of sea
water use 1.10 g cm
3
.
0.14 The atmospheric pressure on the surface of Mars,
where g = 3.7 m s
2
, is only 0.0060 atm. To what extent is
that low pressure due to the low gravitational attraction and
not to the thinness of the atmosphere? What pressure would
the same atmosphere exert on Earth, where g = 9.81 m s
2
?
0.15 What pressure difference must be generated across
the length of a 15 cm vertical drinking straw in order to drink
a water-like liquid of mass density 1.0 g cm
3
(a) on Earth,
(b) on Mars. For data, see Example 0.14.
0.16 The unit 1 millimetre of mercury (1 mmHg) has been
replaced by the unit 1 torr (1 Torr): 1 mmHg is defined as the
pressure at the base of a column of mercury exactly 1 mm
high when its density is 13.5951 g cm
3
and the acceleration
of free fall is 9.806 65 m s
2
. What is the relation between the
two units?
0.17 Suppose that the pressure unit 1 millimetre of water
(1 mmH
2
O) is defined as the pressure at the base of a column
of water of mass density 1000 kg m
3
in a standard gravita-
tional field. Express 1 mmH
2
O in (a) pascals, (b) torr.
0.18 Given that the Celsius and Fahrenheit temperature scales
are related by q
Celsius
/ C = (q
Fahrenheit
/ F 32), what is the
temperature of absolute zero (T = 0) on the Fahrenheit scale?
0.19 In his original formulation, Anders Celsius identified 0
with the boiling point of water and 100 with its freezing point.
Find a relation (expressed like eqn 0.8) between this original
scale (denote it q/ C ) and (a) the current Celsius scale (q/C),
(b) the Fahrenheit scale.
0.20 Imagine that Pluto is inhabited and that its scientists
use a temperature scale in which the freezing point of liquid
nitrogen is 0P (degrees Plutonium) and its boiling point is
5
9
100P. The inhabitants of Earth report these temperatures
as 209.9C and 195.8C, respectively. What is the relation
between temperatures on (a) the Plutonium and Kelvin
scales, (b) the Plutonium and Fahrenheit scales?
0.21 The Rankine scale is used in some engineering applica-
tions. On it, the absolute zero of temperature is set at zero
but the size of the Rankine degree (R) is the same as that of
the Fahrenheit degree (F). What is the boiling point of water
on the Rankine scale?
0.22 Calculate the amount of C
6
H
12
O
6
molecules in 10.0 g of
glucose.
0.23 The density of octane (which we take to model gasoline)
is 0.703 g cm
3
; what amount (in moles) of octane molecules
do you get when you buy 1.00 dm
3
(1.00 litre) of gasoline?
0.24 The molar mass of the oxygen-storage protein myo-
globin is 16.1 kg mol
1
. How many myoglobin molecules are
present in 1.0 g of the compound?
0.25 The mass of a red blood cell is about 33 pg (where
1 pg = 10
12
g), and it contains typically 3 10
8
haemoglobin
molecules. Each haemoglobin molecule is a tetramer of myo-
globin (see preceding exercise). What fraction of the mass of
the cell is due to haemoglobin?
0.26 Express the mass density of a compound, which is
defined as r = m/V, in terms of its molar mass and its molar
volume.
0.27 A sugar (sucrose, C
12
H
22
O
11
) cube has a mass of 5.0 g.
What is the molar concentration of sucrose when one sugar
cube is dissolved in a cup of coffee of volume 200 cm
3
?
0.28 What mass of sodium chloride should be dissolved in
enough water to make 300 cm
3
of 1.00 M NaCl(aq)?
0.29 Use the following data to calculate (a) the molar con-
centration of B in (i) water, (ii) benzene, (b) the molality of B in
(i) water, (ii) benzene.
Mass of B used to make up 100 cm
3
of solution: 2.11 g
Molar mass of B: 234.01 g mol
1
Density of solution in water: 1.01 g cm
3
Density of solution in benzene: 0.881 g cm
3
0.30 Calculate the mole fractions of the molecules of a
mixture that contains 56 g of benzene and 120 g of methyl-
benzene (toluene).
0.31 A simple model of dry air at sea level is that it consists
of 75.53 per cent (by mass) of nitrogen, 23.14 per cent of oxy-
gen, and 1.33 per cent of other substances (principally argon
and carbon dioxide). Calculate the mole fractions of the three
principal substances. Treat other substances as argon.
0.32 Treat air (see the preceding exercise) as a solution of
oxygen in nitrogen. What is the molality of oxygen in air?
0.33 Calculate the mass of carbon dioxide produced by the
combustion of 1.00 dm
3
of gasoline treated as octane of
mass density 0.703 g cm
3
.
INTRODUCTION 14
0.34 What mass of carbon monoxide is needed to reduce
1.0 t of iron(III) oxide to the metal?
Projects
0.35 The gravitational potential energy of a body of mass m
at a distance r from the centre of the Earth is Gmm
E
/r,
where m
E
is the mass of the Earth and G is the gravitational
constant (see inside front cover). Consider the difference in
potential energy of the body when it is moved from the
surface of the Earth (radius r
E
) to a height h above the sur-
face, with h << r
E
, and find an expression for the acceleration
of free fall, g, in terms of the mass and radius of the Earth.
Hint: Use the approximation (1 + h/r
E
)
1
= 1 h/r
E
+
. . .
. See
Appendix 2 for more information on series expansions.
0.37 Use the same approach as in the preceding exercise to
find an approximate expression for moving an electric charge
Q
1
through a distance h from a point r
0
from another charge
Q
2
, with h << r
0
.
Chapter 1
The properties of gases
Equations of state
1.1 The perfect gas equation of state
1.2 Using the perfect gas law
Box 1.1 The gas laws and the weather
1.3 Mixtures of gases: partial pressures
The kinetic model of gases
1.4 The pressure of a gas according to the kinetic
model
1.5 The average speed of gas molecules
1.6 The Maxwell distribution of speeds
1.7 Diffusion and effusion
1.8 Molecular collisions
Real gases
1.9 Molecular interactions
1.10 The critical temperature
1.11 The compression factor
1.12 The virial equation of state
1.13 The van der Waals equation of state
1.14 The liquefaction of gases
CHECKLIST OF KEY IDEAS
TABLE OF KEY EQUATIONS
FURTHER INFORMATION 1.1
QUESTIONS AND EXERCISES
Although gases are simple, both to describe and in
terms of their internal structure, they are of immense
importance. We spend our whole lives surrounded
by gas in the form of air and the local variation in its
properties is what we call the weather. To under-
stand the atmospheres of this and other planets we
need to understand gases. As we breathe, we pump
gas in and out of our lungs, where it changes com-
position and temperature. Many industrial processes
involve gases, and both the outcome of the reaction
and the design of the reaction vessels depend on a
knowledge of their properties.
Equations of state
We can specify the state of any sample of substance
by giving the values of the following properties (all of
which are dened in the Introduction):
V, the volume of the sample
p, the pressure of the sample
T, the temperature of the sample
n, the amount of substance in the sample
However, an astonishing experimental fact is that
these four quantities are not independent of one
another. For instance, we cannot arbitrarily choose
to have a sample of 0.555 mol H
2
O in a volume of
100 cm
3
at 100 kPa and 500 K: it is found experiment-
ally that that state simply does not exist. If we select
the amount, the volume, and the temperature, then
we nd that we have to accept a particular pressure
(in this case, close to 23 MPa). The same is true of all
substances, but the pressure in general will be differ-
ent for each one. This experimental generalization is
summarized by saying the substance obeys an equa-
tion of state, an equation of the form
CHAPTER 1: THE PROPERTIES OF GASES 16
p = f (n,V,T) (1.1)
This expression tells us that the pressure is some
function of amount, volume, and temperature and
that if we know those three variables, then the pres-
sure can have only one value.
The equations of state of most substances are
not known, so in general we cannot write down an
explicit expression for the pressure in terms of the
other variables. However, certain equations of state
are known. In particular, the equation of state of a
low-pressure gas is known, and proves to be very
simple and very useful. This equation is used to
describe the behaviour of gases taking part in reac-
tions, the behaviour of the atmosphere, as a starting
point for problems in chemical engineering, and even
in the description of the structures of stars.
1.1 The perfect gas equation of state
The equation of state of a low-pressure gas was
among the rst results to be established in physical
chemistry. The original experiments were carried
out by Robert Boyle in the seventeenth century and
there was a resurgence in interest later in the cen-
tury when people began to y in balloons. This tech-
nological progress demanded more knowledge about
the response of gases to changes of pressure and
temperature and, like technological advances in
other elds today, that interest stimulated a lot of
experiments.
The experiments of Boyle and his successors led to
the formulation of the following perfect gas equation
of state:
pV = nRT (1.2)
In this equation (which has the form of eqn 1.1 when
we rearrange it into p = nRT/V), the gas constant, R,
is an experimentally determined quantity that turns
out to have the same value for all gases. It may be
determined by evaluating R = pV/nRT as the pres-
sure is allowed to approach zero or by measuring the
speed of sound (which depends on R). Values of R in
different units are given in Table 1.1.
The perfect gas equation of statemore briey,
the perfect gas lawis so-called because it is an
idealization of the equations of state that gases actu-
ally obey. Specically, it is found that all gases obey
the equation ever more closely as the pressure is re-
duced towards zero. That is, eqn 1.2 is an example of
a limiting law, a law that becomes increasingly valid
as the pressure is reduced and is obeyed exactly in the
limit of zero pressure.
A hypothetical substance that obeys eqn 1.2 at all
pressures is called a perfect gas. From what has just
been said, an actual gas, which is termed a real gas,
behaves more and more like a perfect gas as its
pressure is reduced towards zero. In practice, normal
atmospheric pressure at sea level (p 100 kPa) is
already low enough for most real gases to behave
almost perfectly, and unless stated otherwise we
shall always assume in this text that the gases we
encounter behave like a perfect gas. The reason why
a real gas behaves differently from a perfect gas can
be traced to the attractions and repulsions that exist
between actual molecules and that are absent in a
perfect gas (Chapter 15).
A note on good practice A perfect gas is widely called an
ideal gas and the perfect gas equation of state is commonly
called the ideal gas equation We use perfect gas to imply
the absence of molecular interactions; we use ideal in
Chapter 6 to denote mixtures in which all the molecular inter-
actions are the same but not necessarily zero.
The perfect gas law summarizes three sets of ex-
perimental observations. One is Boyles law:
At constant temperature, the pressure of a xed
amount of gas is inversely proportional to its
volume.
Mathematically:
Boyles law: at constant temperature,
We can easily verify that eqn 1.2 is consistent with
Boyles law: by treating n and T as constants, the
perfect gas law becomes pV = constant, and hence
p 1/V. Boyles law implies that if we compress
(reduce the volume of) a xed amount of gas at con-
stant temperature into half its original volume, then
its pressure will double. Figure 1.1 shows the graph
obtained by plotting experimental values of p against
V for a xed amount of gas at different temperatures

p
V

1
Table 1.1
The gas constant in various units
R = 8.314 47 J K
1
mol
1
8.314 47 dm
3
kPa K
1
mol
1
8.205 74 10
2
dm
3
atm K
1
mol
1
62.364 dm
3
Torr K
1
mol
1
1.987 21 cal K
1
mol
1
1 dm
3
= 10
3
m
3
The texts website contains links to online databases of
properties of gases.
EQUATIONS OF STATE 17
and the curves predicted by Boyles law. Each curve
is called an isotherm because it depicts the variation
of a property (in this case, the pressure) at a single
constant temperature. It is hard, from this graph,
to judge how well Boyles law is obeyed. However,
when we plot p against 1/V, we get straight lines, just
as we would expect from Boyles law (Fig. 1.2).
A note on good practice It is generally the case that a pro-
posed relation is easier to verify if the experimental data are
plotted in a form that should give a straight line. That is, the
expression being plotted should have the form y = mx + b,
where m and b are the slope and y-intercept of the line,
respectively. For more information, see Appendix 2.
The second experimental observation summarized
by eqn 1.2 is Charless law:
At constant pressure, the volume of a xed amount
of gas varies linearly with the temperature.
Mathematically:
Charless law: at constant pressure, V = A + B
where (theta) is the temperature on the Celsius
scale and A and B are constants that depend on the
amount of gas and the pressure. Figure 1.3 shows
typical plots of volume against temperature for a
series of samples of gases at different pressures and
conrms that (at low pressures, and for temperatures
that are not too low) the volume varies linearly with
the Celsius temperature. We also see that all the vol-
umes extrapolate to zero as approaches the same
very low temperature (273.15C, in fact), regard-
less of the identity of the gas. Because a volume
cannot be negative, this common temperature must
represent the absolute zero of temperature, a temper-
ature below which it is impossible to cool an object.
Indeed, the thermodynamic scale ascribes the value
T = 0 to this absolute zero of temperature. In terms of
1/Volume, 1/V
P
r
e
s
s
u
r
e
,
p
Observed
Perfect gas
Fig. 1.2 A good test of Boyles law is to plot the pressure
against 1/V (at constant temperature), when a straight line
should be obtained. This diagram shows that the observed
pressures (the blue line) approach a straight line as the vol-
ume is increased and the pressure reduced. A perfect gas
would follow the straight line at all pressures; real gases obey
Boyles law in the limit of low pressures.
Increasing
temperature
Volume, V
P
r
e
s
s
u
r
e
,
p
Fig. 1.1 The volume of a gas decreases as the pressure on it
is increased. For a sample that obeys Boyles law and that
is kept at constant temperature, the graph showing the
dependence is a hyperbola, as shown here. Each curve
corresponds to a single temperature, and hence is an iso-
therm. The isotherms are hyperbolas, graphs of xy = constant,
or y = constant/x (see Appendix 2).
interActivity Explore how the pressure of 1.5 mol
CO
2
(g) varies with volume as it is compressed at (a)
273 K, (b) 373 K from 30 dm
3
to 15 dm
3
.
Hint : To solve this and other interActivities, use either math-
ematical software or the Living graphs from the texts web
site.
Temperature, /C
V
o
l
u
m
e
,
V
Observed
Perfect gas
Increasing
pressure
273.15

Fig. 1.3 This diagram illustrates the content and implications
of Charless law, which asserts that the volume occupied
by a gas (at constant pressure) varies linearly with the
temperature. When plotted against Celsius temperatures
(as here), all gases give straight lines that extrapolate to V = 0
at 273.15C. This extrapolation suggests that 273.15C is
the lowest attainable temperature.
CHAPTER 1: THE PROPERTIES OF GASES 18
the thermodynamic temperature, therefore, Charless
law takes the simpler form
Charless law: at constant pressure, V T
It follows that doubling the temperature (such as
from 300 K to 600 K, corresponding to an increase
from 27C to 327C) doubles the volume, provided
the pressure remains the same. Now we can see that
eqn 1.2 is consistent with Charless law. First, we re-
arrange it into V = nRT/p, and then note that when
the amount n and the pressure p are both constant,
we can write V T, as required.
The third feature of gases summarized by eqn 1.2
is Avogadros principle:
At a given temperature and pressure, equal volumes
of gas contain the same numbers of molecules.
That is, 1.00 dm
3
of oxygen at 100 kPa and 300 K
contains the same number of molecules as 1.00 dm
3
of carbon dioxide, or any other gas, at the same
temperature and pressure. The principle implies
that if we double the number of molecules, but keep
the temperature and pressure constant, then the
volume of the sample will double. We can therefore
write:
Avogadros principle: at constant temperature and
pressure, V n
This result follows easily from eqn 1.2 if we treat
p and T as constants. Avogadros suggestion is a
principle rather than a law (a direct summary of
experience), because it is based on a model of a gas,
in this case as a collection of molecules. Even though
there is no longer any doubt that molecules exist, this
relation remains a principle rather than a law.
The molar volume, V
m
, of any substance (not
just a gas) is the volume it occupies per mole of
molecules. It is calculated by dividing the volume of
the sample by the amount of molecules it contains:
(1.3)
With volume in cubic decimetres and amount in
moles, the units of molar volume are cubic decimetres
per mole (dm
3
mol
1
). Avogadros principle implies
that the molar volume of a gas should be the same
for all gases at the same temperature and pressure.
The data in Table 1.2 show that this conclusion is
approximately true for most gases under normal
conditions (normal atmospheric pressure of about
100 kPa and room temperature).
Volume of sample
Amount of substance in sample
V
V
n
m
=
1.2 Using the perfect gas law
Here we review three elementary applications of the
perfect gas equation of state. The rst is the predic-
tion of the pressure of a gas given its temperature, its
chemical amount, and the volume it occupies. The
second is the prediction of the change in pressure
arising from changes in the conditions. The third is
the calculation of the molar volume of a perfect gas
under any conditions. Calculations like these under-
lie more advanced considerations, including the way
that meteorologists understand the changes in the
atmosphere that we call the weather (Box 1.1).
Table 1.2
The molar volumes of gases at standard ambient
temperature and pressure (SATP: 298.15 K and
1 bar)
Gas V
m
/(dm
3
mol
1
)
Perfect gas 24.7896*
Ammonia 24.8
Argon 24.4
Carbon dioxide 24.6
Nitrogen 24.8
Oxygen 24.8
Hydrogen 24.8
Helium 24.8
* At STP (0C, 1 atm), V
m
= 24.4140 dm
3
mol
1
.
Example 1.1
Predicting the pressure of a sample of gas
A chemist is investigating the conversion of atmospheric
nitrogen to usable form by the bacteria that inhabit the
root systems of certain legumes, and needs to know the
pressure in kilopascals exerted by 1.25 g of nitrogen gas
in a flask of volume 250 cm
3
at 20C.
Strategy For this calculation we need to arrange eqn 1.2
(pV = nRT ) into a form that gives the unknown (the pres-
sure, p) in terms of the information supplied:
To use this expression, we need to know the amount of
molecules (in moles) in the sample, which we can obtain
from the mass and the molar mass (by using n = m/M)
and to convert the temperature to the Kelvin scale (by
adding 273.15 to the Celsius temperature). Select the
p
nRT
V
=